The present invention relates to a 1,2,4,-triazole-3-carboxamide compound represented by the formula (I): ##STR4## wherein R represents a straight-chain or branched-chain saturated (C.sub.2 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a cyclic saturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a straight-chain, branched-chain or cyclic unsaturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a group represented by the formula (II): ##STR5## wherein R.sup.1 represents a halogen atom, a (C.sub.1 -C.sub.3)alkyl group, a (C.sub.1 -C.sub.3)alkoxy group or a fluorine-substituted (C.sub.1 -C.sub.3)alkyl group, m is an integer of from 0 to 5 and n is 0 or 1; a straight-chain or branched-chain saturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a straight-chain or branched-chain unsaturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group; an aralkoxy(C.sub.2 -C.sub.6)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); an aralkoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); a [(C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkoxy](C.sub.2 -C.sub.10)alkyl group; or a group represented by the formula (III): ##STR6## wherein p represents an integer of from 1 to 8, a process for producing the same compound and a herbicidal composition containing the 1,2,4-triazole-3-carboxamide compound as an active ingredient.
In order to protect crops such as rice, wheat, corn, etc. against noxious weeds, thereby aiming at an increased yield, it is inevitable to use herbicide (herbicidal composition).
Hitherto, as the herbicidal composition comprising a derivative of 1,5-diphenyl-1H-1,2,4-triazole-3-carboxamide as an active ingredient, for instance, a herbicidal composition comprising as an active ingredient a herbicidally effective amount of a 1,5-disubstituted 1,2,4-triazole-3-carboxamide represented by the formula: ##STR7## wherein R.sup.1 is an alkyl group having 1 to 3 carbon atoms, a trifluoromethyl group, a chlorine atom, a fluorine atom, an iodine atom or a nitro group; R.sup.2 is a methyl group, a chlorine atom or a hydrogen atom and R.sup.3 is a methyl group or hydrogen atom, provided that 1-(4-methylphenyl)-5-phenyl-1,2,4-triazole-3-carboxamide is excluded, together with a herbicidally acceptable carrier or a diluent (refer to U.S. Pat. No. 4,492,597); a 1,2,4-triazole derivative represented by the formula: ##STR8## wherein R.sup.1 is a hydrogen atom, an alkyl group or a hydroxyalkyl group; R.sup.2 is a hydrogen atom, an alkyl group, a halogenoalkyl group, a hydroxyalkyl group, a cyanoalkyl group, an acetyl group, a halogenoacetyl group, a methoxyacetyl group, an amino group, a methoxy group or a hydroxy group and R.sup.3 and R.sup.4 respectively represent a hydrogen atom, an alkyl group or a halogen atom [refer to Japanese Patent Application Laying-Open (KOKAI) No. 58-194866 (1983)]; and a herbicidal composition containing a derivative of 1,2,4-triazole represented by the general formula: ##STR9## wherein R.sup.1 represents a hydrogen or halogen atom or a C.sub.1 or C.sub.2 alkyl group; R.sup.2 represents a hydrogen or halogen atom or a C.sub.1 or C.sub.2 alkyl, halogeno(C.sub.1 -C.sub.3)alkyl, methoxy, cyano, methoxymethyl, methylthio, methoxycarbonyl or isopropoxycarbonyl group; and R.sup.3 represents a thioamide group or a group represented by the general formula: ##STR10## wherein R.sup.4 represents a hydrogen atom or a C.sub.1 or C.sub.2 alkyl or hydroxy (C.sub.1 or C.sub.2 alkyl) group and R.sup.5 represents a hydrogen atom or a C.sub.1 or C.sub.2 alkyl, halogeno (C.sub.1 or C.sub.2 alkyl), hydroxy (C.sub.1 or C.sub.2 alkyl), cyanomethyl, acetyl, halogenoacetyl, methoxyacetyl, amino, phenyl, methoxy, hydroxyl, C.sub.2 or C.sub.3 alkenyl, halogeno (C.sub.2 or C.sub.3 alkenyl), isopropylcarbonyl, methylthiocarbonyl or 2-methoxyethyl group (GB No. 2120665A) have been proposed.
However, the herbicidal composition containing the above-mentioned compound as an active ingredient can not be satisfied in its herbicidal activity and accordingly, an offer of a herbicide (herbicidal composition) which kills only weeds without causing any injury to crop plants even when it is applied onto crop plants and weeds at the same time, in other words, which has a high selective toxicity, has been strongly demanded.
As a result of the present inventors' studies for obtaining a compound which shows an excellent herbicidal activity and at the same time, does not cause any injury to crop plants, it has been found by the present inventors that 1,2,4-triazole-3-carboxamide represented by the formula (I) has an excellent selective herbicidal activity, and on the basis of their finding, the present inventors have completed the present invention.
The compound represented by the formula (I) is different from the known compounds as the above-mentioned herbicidal ingredient in the point that the compound represented by the formula (I) has a group --CH.sub.2 --O--R [R is the same as in the formula (I)].
In this connection, although the above-mentioned GB No. 2120665 A exemplifies a compound having a --CH.sub.2 OCH.sub.3 group on the phenyl group of 1-position of triazole, the herbicidal activity thereof is far inferior as compared to that of the compound represented by the formula (I).
Accordingly, an object of the present invention is to provide 1,2,4-triazole-3-carboxamide represented by the formula (I) which has a selective herbicidal activity, namely, which shows an excellent herbicidal activity against gramineous plants and broad-leaved plants, particularly broad-leaved plants and on the other hand, does not show any phytotoxicity to crop plants such as rice, wheat, corn, etc. and a herbicidal composition comprising the compound represented by the formula (I) as an active ingredient as well as a process for producing the compound represented by the formula (I). cl SUMMARY OF THE INVENTION
In a first aspect of the present invention, there is provided 1,2,4-triazole-3-carboxamide compound represented by the formula (I): ##STR11## wherein R represents a straight-chain or branched-chain saturated (C.sub.2 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a cyclic saturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a straight-chain, branched-chain or cyclic unsaturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a group represented by the formula (II): ##STR12## wherein R.sup.1 represents a halogen atom, a (C.sub.1 -C.sub.3)alkyl group, a (C.sub.1 -C.sub.3)alkoxy group or a fluorine-substituted (C.sub.1 -C.sub.3)alkyl group, m is an integer of from 0 to 5 and n is 0 or 1; a straight-chain or branched-chain saturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a straight-chain or branched-chain unsaturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group; an aralkoxy(C.sub.2 -C.sub.6)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); an aralkoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); a [(C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkoxy](C.sub.2 -C.sub.10)alkyl group; or a group represented by the formula (III): ##STR13## wherein p represents an integer of from 1 to 8.
In a second aspect of the present invention, there is provided a process for producing a compound 1,2,4-triazole-3-carboxamide, represented by the formula (I): ##STR14## wherein R represents a straight-chain or branched-chain saturated (C.sub.2 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a cyclic saturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a straight-chain, branched-chain or cyclic unsaturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a group represented by the formula (II): ##STR15## wherein R.sup.1 represents a halogen atom, a (C.sub.1 -C.sub.3)alkyl group, a (C.sub.1 -C.sub.3)alkoxy group or a fluorine-substituted (C.sub.1 -C.sub.3)alkyl group, m is an integer of from 0 to 5 and n is 0 or 1; a straight-chain or branched-chain saturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a straight-chain or branched-chain unsaturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group; an aralkoxy(C.sub.2 -C.sub.6)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); an aralkoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); a [(C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkoxy](C.sub.2 -C.sub.10)alkyl group; or a group represented by the formula (III): ##STR16## wherein p is an integer of from 1 to 8, which process comprises the steps of:
reacting a compound represented by the formula (VII): ##STR17## with ammonia at a temperature in the range of from -20.degree. C. to room temperature, thereby obtaining a compound represented by the formula (IV): ##STR18## and reacting the thus obtained compound represented by the formula (IV) with a compound represented by the formula: R--OH wherein R is the same as in the formula (I), in the presence of an inorganic- or organic base at a temperature in the range of from -20.degree. C. to 50.degree. C.
In a third aspect of the present invention, there is provided a process for producing a compound, 1,2,4-triazole-3-carboxamide, represented by the formula (I): ##STR19## wherein R is as defined above, which process comprises the step of reacting a compound represented by the formula (VII): ##STR20## with an amount more than one equivalent of a compound represented by the formula: R--OM wherein R is the same as in the formula (I) and M is a sodium atom or potassium atom, at a temperature in the range of from 0.degree. to 100.degree. C., thereby obtaining a compound represented by the formula: ##STR21## wherein R is as defined above, subjecting the thus obtained compound to hydrolysis, thereby obtaining a compound represented by the formula (VIII): ##STR22## wherein R is as defined above, reacting the thus obtained compound represented by the formula (VIII) with thionyl chloride at a temperature of from 60.degree. to 100.degree. C., thereby obtaining a compound represented by the formula: ##STR23## wherein R is as defined above, and reacting the thus obtained compound with ammonia at a temperature in the range of from -20.degree. C. to room temperature.
In a fourth aspect of the present invention, there is provided a process for producing a compound, 1,2,4-triazole-3-carboxamide represented by the formula (I): ##STR24## wherein R is as defined above, which process comprises the steps of:
(1) reacting 3-aminobenzyl alcohol with sodium nitrite at a temperature of not more than 15.degree. C. in the presence of hydrochloric acid, sulfuric acid or fluoroboric acid, thereby obtaining a diazonium salt represented by the formula: ##STR25## wherein X is Cl, 1/2 (SO.sub.4) or BF.sub.4,
(2) reacting the thus obtained diazonium salt with 2-phenyl-2-oxazolin-5-one represented by the formula: ##STR26## at a temperature of not more than 60.degree. C., thereby obtaining 4-[3-(hydroxymethyl)phenylhydrazono]-2-phenyl-2-oxazolin-5-one represented by the formula (VI): ##STR27##
(3) after adding an amount of more than one equivalent of sodium hydroxide to the thus obtained 4-[3-(hydroxymethyl)phenylhydrazono]-2-phenyl-2-oxazolin-5-one represented by the formula (VI) in an aprotic organic solvent and reacting, adding hydrochloric acid to the thus obtained reaction mixture and heating at a temperature of not more than 100.degree. C., thereby obtaining 1-[3-(hydroxymethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid represented by the formula (V): ##STR28##
(4) reacting the thus obtained 1-[3-(hydroxymethyl)phenyl]-5-phenyl-1H-1,2,4-triazole-3-carboxylic acid represented by the formula (V) with thionyl chloride at a temperature of from 60.degree. to 100.degree. C., thereby obtaining a compound represented by the formula (VII): ##STR29##
(5) reacting the thus obtained compound represented by the formula (VII) with ammonia at a temperature in the range of from -20.degree. C. to room temperature, thereby obtaining a compound represented by the formula (IV): ##STR30##
(6) reacting the thus obtained compound represented by the formula (IV) with a compound represented by the formula: R--OH wherein R is the same as in the formula (I), at a temperature in the range of from -20.degree. to 50.degree. C. in the presence of an inorganic base or organic base.
In a fifth aspect of the present invention, there is provided a herbicidal composition comprising a herbicidally effective amount of a 1,2,4-triazole-3-carboxamide compound represented by the formula (I): ##STR31## wherein R represents a straight-chain or branched-chain saturated (C.sub.2 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a cyclic saturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a straight-chain, branched-chain or cyclic unsaturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a group represented by the formula (II): ##STR32## wherein R.sup.1 represents a halogen atom, a (C.sub.1 -C.sub.3)alkyl group, a (C.sub.1 -C.sub.3)alkoxy group or a fluorine-substituted (C.sub.1 -C.sub.3)alkyl group, m is an integer of from 0 to 5 and n is 0 or 1; a straight-chain or branched-chain saturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a straight-chain or branched-chain unsaturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group; an aralkoxy(C.sub.2 -C.sub.6)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); an aralkoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); a [(C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkoxy](C.sub.2 -C.sub.10)alkyl group; or a group represented by the formula (III): ##STR33## wherein p is an integer of from 1 to 8, and a herbicidally acceptable carrier or adjuvant.
In a sixth aspect of the present invention, there is provided a method for controlling the growth of noxious weeds, which method comprises applying onto noxious weeds or lands a herbicidally effective amount of 1,2,4-triazole-3-carboxamide compound represented by the formula (I): ##STR34## wherein R represents a straight-chain or branched-chain saturated (C.sub.2 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a cyclic saturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a straight-chain, branched-chain or cyclic unsaturated (C.sub.3 -C.sub.10)alkyl group which is unsubstituted or substituted by fluorine atom(s); a group represented by the formula (II): ##STR35## wherein R.sup.1 represents a halogen atom, a (C.sub.1 -C.sub.3)alkyl group, a (C.sub.1 -C.sub.3)alkoxy group or a fluorine-substituted (C.sub.1 -C.sub.3)alkyl group, m is an integer of from 0 to 5 and n is 0 or 1; a straight-chain or branched-chain saturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a straight-chain or branched-chain unsaturated (C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group; an aralkoxy(C.sub.2 -C.sub.6)alkyl group; a phenoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); an aralkoxy(C.sub.2 -C.sub.6)alkyl group having phenyl group(s) substituted by halogen atom(s) or (C.sub.1 -C.sub.3)alkyl group(s); a [(C.sub.1 -C.sub.8)alkoxy(C.sub.2 -C.sub.10)alkoxy](C.sub.2 -C.sub.10)alkyl group; or a group represented by the formula (III): ##STR36## wherein p represents an integer of from 1 to 8.